US5558726A - Cold rolled steel having excellent machinability and production thereof - Google Patents
Cold rolled steel having excellent machinability and production thereof Download PDFInfo
- Publication number
- US5558726A US5558726A US08/481,426 US48142695A US5558726A US 5558726 A US5558726 A US 5558726A US 48142695 A US48142695 A US 48142695A US 5558726 A US5558726 A US 5558726A
- Authority
- US
- United States
- Prior art keywords
- tin
- relation
- rolled steel
- slab
- steel sheet
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/04—Ferrous alloys, e.g. steel alloys containing manganese
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/14—Ferrous alloys, e.g. steel alloys containing titanium or zirconium
-
- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
- C21D8/02—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips
-
- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
- C21D8/02—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips
- C21D8/021—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips involving a particular fabrication or treatment of ingot or slab
-
- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
- C21D8/02—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips
- C21D8/04—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips to produce plates or strips for deep-drawing
- C21D8/041—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips to produce plates or strips for deep-drawing involving a particular fabrication or treatment of ingot or slab
-
- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D9/00—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor
- C21D9/46—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor for sheet metals
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C33/00—Making ferrous alloys
- C22C33/04—Making ferrous alloys by melting
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/06—Ferrous alloys, e.g. steel alloys containing aluminium
-
- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D2211/00—Microstructure comprising significant phases
- C21D2211/004—Dispersions; Precipitations
-
- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
- C21D8/02—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips
- C21D8/0221—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips characterised by the working steps
- C21D8/0226—Hot rolling
-
- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
- C21D8/02—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips
- C21D8/0221—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips characterised by the working steps
- C21D8/0236—Cold rolling
-
- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
- C21D8/02—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips
- C21D8/04—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips to produce plates or strips for deep-drawing
- C21D8/0421—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips to produce plates or strips for deep-drawing characterised by the working steps
- C21D8/0426—Hot rolling
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Definitions
- This invention is directed to remelting of scrap material by an electric furnace, etc., for re-utilizing scrap steel which has been remarkably increasing in recent years from automobile scrap, and so forth. More particularly, the present invention relates to a cold rolled steel sheet having excellent cold formability, though it has a high N content, and to a production method of such a cold rolled steel sheet.
- r value Rankford value
- Japanese Examined Patent Publication (Kokoku) No. 44-18066 discloses a technology which fixes and stabilizes C by adding 0.02 to 0.5% of Ti to a steel containing 0.001 to 0.02% of C and not greater than 0.015% of 0.
- Japanese Examined Patent Publication (Kokoku) No. 3-54186 discloses a method which reduces both C and N contents to at most 0.005% and adds Ti and Nb
- Japanese Examined Patent Publication (Kokoku) No. 53-12899 discloses a technology which minimizes the C and N contents and adds Ti, Nb and B for fixing them.
- Japanese Unexamined Patent Publication (Kokai) No. 57-26124 can be cited as a prior art reference which discloses a production technology of a cold rolled steel sheet having a high N content.
- This technology continuously anneals a cold rolled steel sheet having a specific C, Mn and Al content and containing 30 to 200 ppm of N at a predetermined temperature, and obtains a cold rolled steel sheet having excellent bake-hardenability. Because this cold rolled steel sheet contains a large quantity of N, a content of free N (the balance obtained by subtracting N bonded to Ti, Nb, etc., from the total N content) can be secured. This free N exhibits bake-hardenability.
- the present invention When re-utilizing a scrap and using an electric furnace for this re-utilization, the present invention provides a cold rolled steel sheet having excellent formability, though it has a high N content, and a production method which does not require processing such as vacuum degassing.
- the inventors of the present invention have examined the components of a steel, its crystal structure, the forms of precipitates (kind, amount, distribution condition) and mechanical properties of the steel sheet after cold rolling and annealing.
- An Al killed steel was produced by using an electric furnace. Because it was possible to predict in advance that the N content became high, Ti was added so as to fix N and to make it harmless.
- Steel components in the ladle were 302 ppm of C, 0.009% of Si, 0.163% of Mn, 0.005% of P, 0.0118% of S, 0.0319% of Al, 122 ppm of N, 0.029% of Ti (free N of 37 ppm when Ti is added), 0.015% of Cr, 0.016% of Cu and 0.026% of Ni.
- This steel was cast and hot rolled, cold rolled and annealed under various conditions, then various properties thereof (yield point, tensile strength, elongation, r value) were examined.
- a wide variety of properties could be obtained such as a steel sheet having good formability with a yield point of 16 to 18 kgf/mm 2 , a tensile strength of 30 to 32 kgf/mm 2 , elongation of 44 to 46% and an r value of 1.7 to 1.8 or a steel sheet having very poor formability with a yield point of 18 to 25 kgf/mm 2 , a tensile strength of 37 to 39 kgf/mm 2 , elongation of 36 to 38% and an r value of 1.4 to 1.5.
- the inventors of this invention changed the cooling rate (to various values between 10° C./min and 82° C./min) at the time of casting and examined the relation between the mechanical properties of the steel sheet after annealing and the quantity and form of TiN.
- a material having the same components but having a low N content of 26 ppm hereinafter called the "corresponding material" was treated by the same process, and similar examinations were carried out.
- the heating temperature of the slab was 1,200° C.
- the hot rolling temperature was 880° C.
- the thickness of the hot rolled sheet was 3.5 mm
- the thickness of the cold rolled sheet was 0.8 mm (reduction ratio: 88%)
- the continuous annealing condition was at 820° C. for one minute.
- FIGS. 1(A), 1(B), 1(C) and 1(D) show the relation between the cooling rate at the time of casting and the form of TiN (abscissa) and the resulting material properties (ordinate).
- the length d of one of its sides is used as the size of TiN, and this size of TiN was classified into a group less than 0.05 ⁇ m (hereinafter called the "A rank"), a group of 0.05 to 10 ⁇ m (hereinafter called the “B rank”) and a group exceeding 10 ⁇ m (hereinafter called the "C rank”), and the proportion of each rank was displayed by wt %.
- a rank 0.05 ⁇ m
- B rank a group of 0.05 to 10 ⁇ m
- C rank group exceeding 10 ⁇ m
- FIG. 2 shows a sketch of TiN measured by anelectron microscope. Item (1) described in FIG. 2 shows an example when the size d is about 1 ⁇ m, item (2) described in FIG. 2 shows an example when the size d is about 3 ⁇ m and item (3) described in FIG. 2 shows an example when d is from about 6 to about 7 ⁇ m.
- the present invention forms TiN by adding Ti, makes N harmless by limiting a free N quantity, and drastically improves the mechanical properties such as the yield point, the tensile strength, the r value, etc., by stipulating the size of TiN in a predetermined range.
- the product according to the present invention is a cold rolled steel sheet containing not greater than 0.1% of C, 0.0060 to 0.0150% of N, not greater than 0.4% of Mn which also satisfies the relation Mn/S ⁇ 7, not greater than 0.030% of S, not greater than 0.1% of Al, not greater than 0.08% of Ti which also satisfies the relation Ti:N (%)--Ti/3.42 (%) ⁇ 0.0070, in terms of weight percentage (wt %), and the balance consisting of Fe and unavoidable impurities, wherein the cold rolled steel sheet comprises a texture in which TiN having a size of 0.05 to 10 ⁇ m (by measurement through an electron microscope) is precipitated in weight at least 1/2 of the TiN total weight.
- a molten steel having the chemical components described above is cooled at a temperature in the range of the solidifying point to 600° C. at a rate of 10 to 50° C./min to produce a slab, and after this slab is heated, it is hot rolled. Then, the resulting hog rolled sheet is taken up at a temperature of not lower than 700° C. and is cold rolled. Thereafter, continuous annealing is carried out.
- box annealing of the cold rolled sheet is carried out, the slab is heated at a temperature not lower than 1,130° C., and after hot rolling, the sheet is wound at a temperature not higher than 650° C.
- Ti is added in such an amount that free N in the slab is below 0.0040%, and when box annealing is carried out, free N falls within the range of 0.0020 to 0.0070%.
- B may be added, whenever necessary.
- FIGS. 1(A), 1(B), 1(C) and 1(D) are diagrams showing the relationship between the weight % of classified size of TiN and material properties.
- FIG. 2 is a diagram showing an example of measurement of the size of TiN.
- the upper limit is set to 0.1%.
- the upper limit is not greater than 0.05%.
- Mn is added in such an amount as to satisfy at least the relation Mn/S ⁇ 7.
- the upper limit is set to 0.4%.
- Al is the element which is added for deoxidation and for fixing N which has not been fixed and made harmless by Ti.
- the addition of Al in a great amount lowers elongation, and the upper limit is therefore set to 0.1%, and the lower limit is set to 0.005%. The object described above cannot be accomplished when the amount is less than this lower limit value.
- N is a detrimental element for formability, but its whole amount need not be fixed by Ti and be made harmless. However, the amount of free N which is not fixed by Ti must be stipulated.
- the formula N (%)--Ti/3.42 (%) must be not greater than 0.0070%.
- the value exceeds 0.0070% the precipitation quantity of AlN for fixing excessive free N becomes great, and the grain growth at the process of annealing is impeded. Accordingly, elongation and the r value drop.
- B combines with N and forms BN, and provides the effect of preventing the precipitation of AlN.
- the precipitation state of AlN is susceptible to the influences of the temperature history at hot rolling, and results in variance of properties.
- high temperature winding is preferably carried out in hot rolling. The addition of B can solve this problem, and a cold rolled steel sheet having excellent deep drawability can be produced by continuous annealing without effecting high temperature winding.
- the addition of B in this case is 1.0 ⁇ 1.3 ⁇ B (%)/(N (%)--Ti (%)/3.42) ⁇ 1.5.
- the relation 1.3 ⁇ B (%)/(N (%)--Ti (%)/3.42) represents the atomic ratio of B and free N, and when this value is greater than 1.0, high temperature winding can be omitted.
- B is added in an amount exceeding 1.5 times the amount of free N, elongation and the r value drop. Therefore, the amount should be limited to not greater than 1.5 times.
- the steel substantially comprises Fe with the exception of the components described above, and the steel may contain unavoidable elements which mix from the molten raw materials such as the scrap.
- the molten steel having the components described above is poured into a casting machine such as a continuous casing machine and is cooled to produce a slab.
- cooling is carried out at a cooling rate of 10 to 50° C./min within a temperature range of the solidifying point to 600° C.
- the size of TiN in an amount at least 1/2 of the total weight is made to 0.05 to 10 ⁇ m by this cooling.
- the slab is hot rolled.
- the hot rolling condition is not particularly limited, but in order to obtain a cold rolled steel sheet having high deep drawability by the continuous annealing process, a winding temperature is within the range of not lower than 700° C.
- free N N (%)--Ti/3.42 (%)
- free N is not greater than 0.0040%.
- N is fixed as AlN and is rendered harmless.
- the free N amount is limited to a low level (because the AlN formation time is short) and to precipitate in advance N as AlN by high temperature winding. Further, massing and granulation of the carbides are simultaneously effected by high temperature winding.
- the heating temperature of the slab is set to at least 1.130° C., and the winding temperature is set to be not greater than 650° C.
- N (%)--Ti/3.42 (%) must be from 0.0020 to 0.0070%.
- a minimum 0.0020% of free N is allowed to remain and AlN is allowed to precipitate during the annealing process so that the texture structure can be improved by using this AlN, unlike the case of the production of the rolled sheet by continuous annealing.
- the slab is heated at a high temperature of at least 1,130° C. so as to cause complete solid solution of AlN, and low temperature winding of the hot rolled sheet is carried out so as not to allow AlN to precipitate before the annealing step.
- the cold rolling condition is not particularly limited, and ordinary rolling is carried out to obtain a desired sheet thickness.
- Experiment No. 6 represents the case where free N exceeded the upper limit of claim 1 and elongation was inferior.
- Experiments Nos. 9 and 10 represent the cases where the sizes of TiN were too great and elongation was also inferior.
- Experiments Nos. 11 and 12 represent the cases where the sizes of TiN were too small, so that the yield strength was excessively high and elongation was low.
- Steels Nos. 1, 2, 3, 4, 5, 7 and 8 as the steel of the present invention provided excellent properties (yield strength, tensile strength, elongation, r value).
- B-containing steels having the components shown in Table 5 were hot rolled, cold rolled and annealed under the condition tabulated in Table 6. The properties obtained at this time are also tabulated in Table 6.
- the steel sheets according to the present invention exhibited good formability even after the surface treatment.
- the steel sheets according to the present invention exhibited excellent properties even after the molten zinc plating treatment.
- the plating quantity of molten zinc plating was 100 g/m 2 per surface.
- the steel sheets according to the present invention also exhibited here excellent properties as a steel sheet for a tin plate.
- the present invention can make N harmless where N unavoidably attains a high level when a scrap is reutilized, and can obtain a cold rolled steel sheet having high formability irrespective of a high N content.
- the cold rolled steel sheet according to the present invention can be utilized not only as the cold rolled steel sheet but also as a raw sheet for a surface treated steel sheet such as a molten zinc plated steel sheet, an electrogalvanized steel sheet, an electrotin plated steel sheet, and so forth. Accordingly, the present invention has an extremely great industrial value.
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Crystallography & Structural Chemistry (AREA)
- Heat Treatment Of Sheet Steel (AREA)
- Heat Treatment Of Steel (AREA)
Abstract
PCT No. PCT/JP94/01752 Sec. 371 Date Jun. 14, 1995 Sec. 102(e) Date Jun. 14, 1995 PCT Filed Oct. 18, 1994 PCT Pub. No. WO95/11320 PCT Pub. Date Apr. 27, 1995This invention aims at obtaining a cold steel sheet having excellent cold formability irrespective of a high N content in order to re-utilize a scrap steel generated from scraps. A steel sheet comprising not greater than 0.1% of C, 60 to 150 ppm of N, not greater than 0.4% of Mn satisfying the relation Mn/S>/=7, not greater than 0.030% of S, not greater than 0.1% of Al and not greater than 0.08% of Ti satisfying the relation N (%)-Ti/3.42 (%)</=0.007, wherein the size of TiN in the weight at least +E,fra 1/2+EE of the total TiN weight is 0.05 to 10 mu m, is obtained. When production is made by continuous annealing, Ti is added so as to satisfy the relation N (%)-Ti/3.42 (%)</=0.004% and furthermore, high temperature winding is effected in hot rolling or B is added. When production is made by box annealing, the Ti content is adjusted so as to satisfy the relation 0.002%</=N (%)-Ti/3.42 (%)</=0.007%, a slab heating temperature is set to a higher temperature and the winding temperature of a hot rolled sheet is set to a lower temperature.
Description
This invention is directed to remelting of scrap material by an electric furnace, etc., for re-utilizing scrap steel which has been remarkably increasing in recent years from automobile scrap, and so forth. More particularly, the present invention relates to a cold rolled steel sheet having excellent cold formability, though it has a high N content, and to a production method of such a cold rolled steel sheet.
Recently, quality of a cold rolled steel sheet for forming and its production technologies have made remarkable progress, and particularly, a Rankford value (hereinafter referred to as the "r value") representing deep drawability when cold has become as high as 1.7 or more.
As a technology for obtaining such high performance, Japanese Examined Patent Publication (Kokoku) No. 44-18066 discloses a technology which fixes and stabilizes C by adding 0.02 to 0.5% of Ti to a steel containing 0.001 to 0.02% of C and not greater than 0.015% of 0.
Japanese Examined Patent Publication (Kokoku) No. 3-54186 discloses a method which reduces both C and N contents to at most 0.005% and adds Ti and Nb, and Japanese Examined Patent Publication (Kokoku) No. 53-12899 discloses a technology which minimizes the C and N contents and adds Ti, Nb and B for fixing them.
These prior art technologies are based on the common technical concept of reducing the C and N contents as much as possible and obtain a cold rolled steel sheet having excellent non-ageability and excellent cold formability.
Re-utilization of steel scrap which is generated in large quantities everywhere has become a very important problem at present. To re-utilize the scrap, it is common to arc melt the scrap by an electric furnace, or the like. In this case, the N content in the steel reaches a high level of 60 ppm or more because N2 in the air comes into the steel.
When the N content is great, formability drops remarkably. Particularly in a high nitrogen region having an N content of 60 ppm or more, forming involving large deformation such as deep drawing becomes hardly possible. Means such as vacuum degassing must be employed in order to reduce this nitrogen content, and the production cost unavoidably increases.
Japanese Unexamined Patent Publication (Kokai) No. 57-26124 can be cited as a prior art reference which discloses a production technology of a cold rolled steel sheet having a high N content. This technology continuously anneals a cold rolled steel sheet having a specific C, Mn and Al content and containing 30 to 200 ppm of N at a predetermined temperature, and obtains a cold rolled steel sheet having excellent bake-hardenability. Because this cold rolled steel sheet contains a large quantity of N, a content of free N (the balance obtained by subtracting N bonded to Ti, Nb, etc., from the total N content) can be secured. This free N exhibits bake-hardenability. This reference discloses also that when this steel sheet is allowed to contain P, Si and Ti, its strength can also be improved. Nonetheless, Japanese Unexamined Patent Publication (Kokai) No. 57-26124 does not at all disclose a technology for securing formability of a high N steel.
As means for solving this problem, the inventors of the present invention invented, and filed a patent application for, a high N content hot rolled steel sheet having high strength and high formability and a production technology thereof in Japanese Patent Application No. 4-292352. This reference allows a high N (50 to 150 ppm) steel to contain C so that the carbon equivalent becomes 0.1 to 0.45%, secures an area fraction of pearlite of at least 5% so as to secure uniform elongation after cold forming, and disperses TiN of which sizes 1 μm or more in a weight proportion of 0.0008 to 0.015% so as to obtain a hot rolled steel sheet having a tensile strength of 34 kgf/mm2 or more.
However, this reference does not at all suggest formability of a high N cold rolled steel sheet.
When re-utilizing a scrap and using an electric furnace for this re-utilization, the present invention provides a cold rolled steel sheet having excellent formability, though it has a high N content, and a production method which does not require processing such as vacuum degassing.
The inventors of the present invention have examined the components of a steel, its crystal structure, the forms of precipitates (kind, amount, distribution condition) and mechanical properties of the steel sheet after cold rolling and annealing.
First of all, the experimental results which have resulted in completion of the present invention will be explained.
An Al killed steel was produced by using an electric furnace. Because it was possible to predict in advance that the N content became high, Ti was added so as to fix N and to make it harmless. Steel components in the ladle were 302 ppm of C, 0.009% of Si, 0.163% of Mn, 0.005% of P, 0.0118% of S, 0.0319% of Al, 122 ppm of N, 0.029% of Ti (free N of 37 ppm when Ti is added), 0.015% of Cr, 0.016% of Cu and 0.026% of Ni.
This steel was cast and hot rolled, cold rolled and annealed under various conditions, then various properties thereof (yield point, tensile strength, elongation, r value) were examined.
More concretely, a wide variety of properties could be obtained such as a steel sheet having good formability with a yield point of 16 to 18 kgf/mm2, a tensile strength of 30 to 32 kgf/mm2, elongation of 44 to 46% and an r value of 1.7 to 1.8 or a steel sheet having very poor formability with a yield point of 18 to 25 kgf/mm2, a tensile strength of 37 to 39 kgf/mm2, elongation of 36 to 38% and an r value of 1.4 to 1.5.
On the assumption that variance of these properties was primarily associated with the quantities of the precipitates consisting principally of TiN and their forms (size, dispersion state), the inventors of this invention changed the cooling rate (to various values between 10° C./min and 82° C./min) at the time of casting and examined the relation between the mechanical properties of the steel sheet after annealing and the quantity and form of TiN. In addition, a material having the same components but having a low N content of 26 ppm (hereinafter called the "corresponding material") was treated by the same process, and similar examinations were carried out.
Incidentally, the heating temperature of the slab was 1,200° C., the hot rolling temperature was 880° C., the thickness of the hot rolled sheet was 3.5 mm, the thickness of the cold rolled sheet was 0.8 mm (reduction ratio: 88%) and the continuous annealing condition was at 820° C. for one minute.
Inspection of dozens of fields per sample was carried out for inclusions such as TiN, etc., by using an electronmicroscope, and the size distribution of TiN and the weight distribution on the basis of the former were determined. FIGS. 1(A), 1(B), 1(C) and 1(D) show the relation between the cooling rate at the time of casting and the form of TiN (abscissa) and the resulting material properties (ordinate).
Since the shape of the precipitate of TiN is substantially square, the length d of one of its sides is used as the size of TiN, and this size of TiN was classified into a group less than 0.05 μm (hereinafter called the "A rank"), a group of 0.05 to 10 μm (hereinafter called the "B rank") and a group exceeding 10 μm (hereinafter called the "C rank"), and the proportion of each rank was displayed by wt %.
In the drawing, when the cooling rate at the time of casting was great (82° C./min), both yield point and tensile strength became great while the r value was extremely small, and cold forming was extremely difficult. TiN at this time was all in the A rank. As the cooling rate at the time of casting was decreased (38° C./min), the yield point and the tensile strength gradually dropped while the elongation and the r value increased, so that cold machinability was improved. When the cooling rate at the time of casting was further lowered (7° C./min), the yield point increased somewhat, the tensile strength dropped somewhat, and the elongation as well as the r value dropped. In conjunction with the size distribution of TiN, good machinability could not be obtained when the size of the A rank was too great or when the size of the C rank was too great, and formability equivalent to that of the corresponding material could be obtained when the size of the B rank was at least 50%.
The reasons are assumed as follows. When the cooling rate at the process of casting is high, TiN below 0.05 μm finely precipitates, impedes the grain growth at the time of annealing and provides the action of precipitation hardening. As a result, elongation or the r value is remarkably deteriorated. When the cooling rate at the process of casting is low, on the other hand, a large amount of TiN exceeding 10 μm precipitates, and cracks occur from such great inclusions in the cast.
Accordingly, elongation is mainly deteriorated. FIG. 2 shows a sketch of TiN measured by anelectron microscope. Item (1) described in FIG. 2 shows an example when the size d is about 1 μm, item (2) described in FIG. 2 shows an example when the size d is about 3 μm and item (3) described in FIG. 2 shows an example when d is from about 6 to about 7 μm.
In other words, in order to obtain a cold rolled sheet having high formability from the starting material having a high N content, the present invention forms TiN by adding Ti, makes N harmless by limiting a free N quantity, and drastically improves the mechanical properties such as the yield point, the tensile strength, the r value, etc., by stipulating the size of TiN in a predetermined range.
Accordingly, the product according to the present invention is a cold rolled steel sheet containing not greater than 0.1% of C, 0.0060 to 0.0150% of N, not greater than 0.4% of Mn which also satisfies the relation Mn/S≧7, not greater than 0.030% of S, not greater than 0.1% of Al, not greater than 0.08% of Ti which also satisfies the relation Ti:N (%)--Ti/3.42 (%)≦0.0070, in terms of weight percentage (wt %), and the balance consisting of Fe and unavoidable impurities, wherein the cold rolled steel sheet comprises a texture in which TiN having a size of 0.05 to 10 μm (by measurement through an electron microscope) is precipitated in weight at least 1/2 of the TiN total weight.
To obtain such a cold rolled steel sheet, a molten steel having the chemical components described above is cooled at a temperature in the range of the solidifying point to 600° C. at a rate of 10 to 50° C./min to produce a slab, and after this slab is heated, it is hot rolled. Then, the resulting hog rolled sheet is taken up at a temperature of not lower than 700° C. and is cold rolled. Thereafter, continuous annealing is carried out. Incidentally, when box annealing of the cold rolled sheet is carried out, the slab is heated at a temperature not lower than 1,130° C., and after hot rolling, the sheet is wound at a temperature not higher than 650° C.
When continuous annealing is carried out, Ti is added in such an amount that free N in the slab is below 0.0040%, and when box annealing is carried out, free N falls within the range of 0.0020 to 0.0070%. To fix N, B may be added, whenever necessary.
FIGS. 1(A), 1(B), 1(C) and 1(D) are diagrams showing the relationship between the weight % of classified size of TiN and material properties; and
FIG. 2 is a diagram showing an example of measurement of the size of TiN.
Hereinafter, the best mode for carrying out the present invention will be described in detail.
First, the reasons for limitation of the chemical components in the present invention will be explained.
Since C improves the strength of the steel but lowers its cold formability (elongation, drawability), its upper limit is set to 0.1%. Preferably, the upper limit is not greater than 0.05%.
In order to make S harmless, Mn is added in such an amount as to satisfy at least the relation Mn/S≧7. However, when Mn is added in an excessive amount, it deteriorates formability (elongation, deep drawability). Accordingly, the upper limit is set to 0.4%.
S induces red heat brittleness during hot rolling and causes the occurrence of cracks. Therefore, its upper limit is set to 0.03%.
Al is the element which is added for deoxidation and for fixing N which has not been fixed and made harmless by Ti. However, the addition of Al in a great amount lowers elongation, and the upper limit is therefore set to 0.1%, and the lower limit is set to 0.005%. The object described above cannot be accomplished when the amount is less than this lower limit value.
N is a detrimental element for formability, but its whole amount need not be fixed by Ti and be made harmless. However, the amount of free N which is not fixed by Ti must be stipulated.
In other words, the formula N (%)--Ti/3.42 (%) must be not greater than 0.0070%. When the value exceeds 0.0070%, the precipitation quantity of AlN for fixing excessive free N becomes great, and the grain growth at the process of annealing is impeded. Accordingly, elongation and the r value drop.
As described above, Ti is added so as to fix N and to make it harmless, but an amount satisfying at least the relation N (%)--Ti/3.42 (%)≦0.0070% is necessary. However, excessive Ti bonds with C and TiC precipitates if the amount of addition is too great. In such a case, elongation and the r value become deteriorated. Accordingly, the upper limit is set to 0.08%.
B combines with N and forms BN, and provides the effect of preventing the precipitation of AlN. In the production method by continuous annealing, the precipitation state of AlN is susceptible to the influences of the temperature history at hot rolling, and results in variance of properties. To avoid this problem, high temperature winding is preferably carried out in hot rolling. The addition of B can solve this problem, and a cold rolled steel sheet having excellent deep drawability can be produced by continuous annealing without effecting high temperature winding.
The addition of B in this case is 1.0≦1.3×B (%)/(N (%)--Ti (%)/3.42)≦1.5. In other words, the relation 1.3×B (%)/(N (%)--Ti (%)/3.42) represents the atomic ratio of B and free N, and when this value is greater than 1.0, high temperature winding can be omitted. When B is added in an amount exceeding 1.5 times the amount of free N, elongation and the r value drop. Therefore, the amount should be limited to not greater than 1.5 times.
In the present invention, the steel substantially comprises Fe with the exception of the components described above, and the steel may contain unavoidable elements which mix from the molten raw materials such as the scrap.
Next, the production condition will be described.
The molten steel having the components described above is poured into a casting machine such as a continuous casing machine and is cooled to produce a slab. In this case, cooling is carried out at a cooling rate of 10 to 50° C./min within a temperature range of the solidifying point to 600° C. The size of TiN in an amount at least 1/2 of the total weight is made to 0.05 to 10 μm by this cooling.
Next, after being heated within an ordinary temperature range, the slab is hot rolled. The hot rolling condition is not particularly limited, but in order to obtain a cold rolled steel sheet having high deep drawability by the continuous annealing process, a winding temperature is within the range of not lower than 700° C. In this case, free N (N (%)--Ti/3.42 (%)) is not greater than 0.0040%. For, when free N is below 0.0040%, N is fixed as AlN and is rendered harmless.
In order to particularly secure deep drawability for the steel sheet produced by the continuous annealing process, it is preferred to limit the free N amount to a low level (because the AlN formation time is short) and to precipitate in advance N as AlN by high temperature winding. Further, massing and granulation of the carbides are simultaneously effected by high temperature winding.
Incidentally, when B is added as described above, precipitation of AlN is not necessary, and high temperature winding of the hot rolled sheet can be omitted.
To obtain a cold rolled steel sheet having high deep drawability by the box annealing process, the heating temperature of the slab is set to at least 1.130° C., and the winding temperature is set to be not greater than 650° C. In this case, N (%)--Ti/3.42 (%) must be from 0.0020 to 0.0070%. In other words, to secure deep drawability for the rolled sheet by the box annealing process, a minimum 0.0020% of free N is allowed to remain and AlN is allowed to precipitate during the annealing process so that the texture structure can be improved by using this AlN, unlike the case of the production of the rolled sheet by continuous annealing. Accordingly, the slab is heated at a high temperature of at least 1,130° C. so as to cause complete solid solution of AlN, and low temperature winding of the hot rolled sheet is carried out so as not to allow AlN to precipitate before the annealing step.
The cold rolling condition is not particularly limited, and ordinary rolling is carried out to obtain a desired sheet thickness.
Although the present invention has been completed on the basis of the cold rolled steel sheet, this technology can also be applied to surface treated steel sheets for containers, for construction and for automobiles as will be represented by the following examples.
Steels having the components tabulated in Table 1 were hot rolled, cold rolled and annealed under the condition tabulated in Table 2. The properties obtained in this instance were also tabulated in Table 2.
Experiment No. 6 represents the case where free N exceeded the upper limit of claim 1 and elongation was inferior. Experiments Nos. 9 and 10 represent the cases where the sizes of TiN were too great and elongation was also inferior. Experiments Nos. 11 and 12 represent the cases where the sizes of TiN were too small, so that the yield strength was excessively high and elongation was low.
Steels Nos. 1, 2, 3, 4, 5, 7 and 8 as the steel of the present invention provided excellent properties (yield strength, tensile strength, elongation, r value).
TABLE 1
__________________________________________________________________________
Free
Si ×
Mn ×
P ×
Al ×
Ti ×
N* TiN**
No.
C ppm
10.sup.-3 %
10.sup.-3 %
10.sup.-3 %
S ppm
10.sup.-3 %
N ppm
10.sup.-3 %
ppm Form
Remarks
__________________________________________________________________________
1 302 9 163 5 118 32 122 29 37 a This invention
2 413 25 210 8 161 55 102 32 8 a This invention
3 501 16 222 6 144 60 82 20 24 a This invention
4 355 10 188 8 142 54 140 25 67 a This invention
5 401 8 155 5 149 35 122 49 -21 a This invention
6 415 8 170 6 135 70 90 -- 90 -- Comp. Example
7 310 9 165 6 121 35 118 29 33 a This invention
8 310 9 165 6 121 35 118 29 33 a This invention
9 410 13 199 6 142 44 109 27 30 b Comp. Example
10 410 13 199 6 142 44 109 27 30 b Comp. Example
11 330 15 188 7 151 46 139 37 31 c Comp. Example
12 330 15 188 7 151 46 139 37 31 c Comp. Example
__________________________________________________________________________
*Free N: total N - Ti/3.42
**TiN form: (a) 0.05 μm ≦ TiN size ≦10 μm was at leas
50% of the tatal amount (b) 10 μm < TiN size was at least 50% of the
total amount (c) TiN size <0.05 μm was at least 50% of the total amoun
The underline represents the portions outside the range of the present
invention.
TABLE 2
__________________________________________________________________________
Processing Condition
Cold Rolling
Hot Rolling Condition
Condition
Thickness Thickness Skin
Slab of Hot
Reduc-
of cold Pass
Heating Winding
Rolled
tion
rolled Roll-
Temp. Temp.
Sheet ratio
sheet Annealing Condition
ing
No.
°C.
°C.
mm % mm System
Cycle %
__________________________________________________________________________
1 1250 550 3.0 73 0.8 Box 680° C. × 14
1.2
2 1150 750 3.5 77 0.8 Con.
820° C. × 1
1.0.
3 1250 550 3.0 73 0.8 Box 680° C. × 14
1.2
4 1250 550 3.0 73 0.8 Box 680° C. × 14
1.2
5 1150 750 3.5 77 0.8 Con.
820° C. × 1
1.0.
6 1250 550 3.0 73 0.8 Box 680° C. × 14
1.2
7 1250 550 3.0 73 0.8 Box 680° C. × 14
1.2
8 1150 750 3.5 77 0.8 Con.
820° C. × 1
1.0.
9 1250 550 3.0 73 0.8 Box 680° C. × 14
1.2
10 1150 750 3.5 77 0.8 Con.
820° C. × 1
1.0.
11 1250 550 3.0 73 0.8 Box 680° C. × 14
1.2
12 1150 750 3.5 77 0.8 Con.
820° C. × 1
1.0.
__________________________________________________________________________
Properties
Yield
Tensile
Elon- This
strength
strength
gation
r invention or
No.
kgf/mm.sup.2
kgf/mm.sup.2
% Value
Comp. Example
__________________________________________________________________________
1 17.1 31.0 46 1.81
This
invention
2 18.1 31.5 45 1.78
This
invention
3 17.2 30.8 46 1.83
This
invention
4 18.4 31.9 43 1.71
This
invention
5 18.9 32.4 42 1.67
This
invention
6 19.7 33.4 38 1.52
Comp. Example
7 17.3 31.0 46 1.79
This
invention
8 17.5 30.7 46 1.81
This
invention
9 17.5 29.8 41 1.66
Comp. Example
10 17.8 30.2 40 1.70
Comp. Example
11 25.1 37.7 36 1.39
Comp. Example
12 25.4 38.0 35 1.42
Comp. Example
__________________________________________________________________________
Annealing System
Con.: Continuous annealing
Box: Box annealing
r Value = (r.sub.L + r.sub.C + 2r.sub.D)/4
Steels having higher Ti contents as shown in Table 3 were hot rolled, cold rolled and annealed under the condition tabulated in Table 4. The properties of the resulting steel sheets were also tabulated in Table 4.
In Experiment No. 14, the Ti amount exceeded the upper limit stipulated in the claims, and the other components and the production condition were the same as those of Experiment No. 13. In comparison with Experiment No. 13 wherein the Ti amount was within the range of the present invention, both elongation and the r value were lower.
TABLE 3
__________________________________________________________________________
Si ×
Mn ×
P ×
Al ×
Ti ×
C 10.sup.-3
10.sup.-3
10.sup.-3
10.sup.-3
N 10.sup.-3
Free N*
TiN**
No.
ppm % % % S ppm
% ppm
% ppm Form
Remarks
__________________________________________________________________________
13 318 9 203 5 240 44 148
74 -68 a This
invention
14 318 9 203 5 240 44 148
92 -121 a This
invention
__________________________________________________________________________
*Free N: total N Ti/3.42
**TiN form: (a) 0.05 μm ≦ TiN size ≦10 μm was at leas
50% of the tatal amount (b) 10 μm < TiN size was at least 50% of the
total amount (c) TiN size <0.05 μm was at least 50% of the total amoun
The underline represents the portions outside the range of the present
invention
TABLE 4
__________________________________________________________________________
Processing Condition
Cold Rolling
Hot Rolling Condition
Condition
Thickness Thickness Skin
Slab of Hot
Reduc-
of cold Pass
Heating Winding
Rolled
tion
rolled Roll-
Temp. Temp.
Sheet ratio
sheet Annealing Condition
ing
No.
°C.
°C.
mm % mm System
Cycle %
__________________________________________________________________________
13 1150 750 3.5 77 0.8 Con.
820° C. × 1
1.0.
14 1150 750 3.5 77 0.8 Con.
820° C. × 1
1.0.
__________________________________________________________________________
Properties
Yield
Tensile
Elon- This
strength
strength
gation
r invention or
No.
kgf/mm.sup.2
kgf/mm.sup.2
% Value
Comp. Example
__________________________________________________________________________
13 22.4 34.2 39 1.65
This
invention
14 27.2 38.6 35 1.48
Comp. Example
__________________________________________________________________________
Annealing System
Con.: Continuous annealing
Box: Box annealing
r Value = (r.sub.L + r.sub.C + 2r.sub.D)/4
B-containing steels having the components shown in Table 5 were hot rolled, cold rolled and annealed under the condition tabulated in Table 6. The properties obtained at this time are also tabulated in Table 6.
All of the steels were within the range of the present invention and exhibited excellent properties. However, the winding temperature of the hot rolled sheet in Experiment No. 17 was below the lower limit of claim 5 stipulating the condition for obtaining a steel sheet having excellent deep drawability by continuous annealing, and its yield point was somewhat higher while the r value was somewhat lower than those of Experiment No. 16 satisfying the condition of claim 5.
In Experiment No. 15 in which B was added, properties substantially equivalent to those of Experiment No. 16, wherein the winding temperature of the hot rolled sheet was within the range of claim 5, could be obtained even when the hot rolled sheet was taken up at a winding temperature below the lower limit of claim 5. In other words, it corresponded to claim 6, and a steel sheet having excellent deep drawability could be obtained by continuous annealing without limiting the winding temperature of the hot rolled sheet, by the addition of B.
TABLE 5
__________________________________________________________________________
Si ×
Mn ×
P ×
Al ×
Ti ×
C 10-3
10-3
10-3
S 10-3
N 10-3
B Free N*
TiN**
No.
ppm
% % % ppm
% ppm
% ppm
ppm Form
Remarks
__________________________________________________________________________
15 432
9 237 19 125
35 111
31 17 20 a This invention
addition B
16 432
9 237 19 125
35 111
31 17 20 a This invention
addition B
17 302
9 163 5 118
32 122
29 -- 37 a This invention
without addition
__________________________________________________________________________
B
*Free N: total N Ti/3.42
**TiN form: (a) 0.05 μm ≦ TiN size ≦10 μm was at leas
50% of the tatal amount (b) 10 μm < TiN size was at least 50% of the
total amount (c) TiN size <0.05 μm was at least 50% of the total amoun
The underline represents the portions outside the range of the present
invention
TABLE 6
__________________________________________________________________________
Processing Condition
Cold Rolling
Hot Rolling Condition
Condition
Thickness Thickness Skin
Slab of Hot
Reduc-
of cold Pass
Heating Winding
Rolled
tion
rolled Roll-
Temp. Temp.
Sheet ratio
sheet Annealing Condition
ing
No.
°C.
°C.
mm % mm System
Cycle %
__________________________________________________________________________
15 1150 630 3.5 77 0.8 Con.
820° C. × 1
1.0.
16 1150 750 3.5 77 0.8 Con.
820° C. × 1
1.0.
17 1150 630 3.5 77 0.8 Con.
820° C. × 1
1.0.
__________________________________________________________________________
Properties
Yield
Tensile
Elon- This
strength
strength
gation
r invention or
No.
kgf/mm.sup.2
kgf/mm.sup.2
% Value
Comp. Example
__________________________________________________________________________
15 17.8 32.7 45 1.68
This
invention
16 17.4 32.3 46 1.70
This
invention
17 20.2 33.9 42 1.51
This
invention
__________________________________________________________________________
Annealing System
Con.: Continuous annealing
Box: Box annealing
r Value = (r.sub.L + r.sub.C + 2r.sub.D)/4
Steels having the components shown in Table 7 were hot rolled, cold rolled and annealed under the condition tabulated in Table 8, and surface treatment was carried out. Properties obtained in these cases were also tabulated in Table 8.
The steel sheets according to the present invention exhibited good formability even after the surface treatment.
By the way, a plating quantity as 20 g/m2 for one surface in the case of electrogalvanizing, 50 g/m2 for one surface in the case of lead plating, and 20 g/m2 for one surface in the case of electrogalvanizing with an organic coating, and in this case, an organic coating having a thickness of 0.8 μm was applied on the plating.
TABLE 7
__________________________________________________________________________
Si ×
Mn ×
P ×
Al ×
Ti ×
C 10-3
10-3
10-3
S 10-3
N 10-3
B Free N*
TiN**
No.
ppm
% % % ppm
% ppm
% ppm
ppm Form
Remarks
__________________________________________________________________________
18 302
9 163 5 118
32 122
29 -- 37 a This invention
19 302
9 163 5 118
32 122
29 -- 37 a This invention
20 302
9 163 5 118
32 122
29 -- 37 a This invention
21 432
9 237 19 125
35 111
31 17 20 a This invention
22 302
9 163 5 118
32 122
29 -- 37 a This invention
23 302
9 163 5 118
32 122
29 -- 37 a This invention
__________________________________________________________________________
*Free N: total N Ti/3.42
**TiN form: (a) 0.05 μm ≦ TiN size ≦10 μm was at leas
50% of the tatal amount (b) 10 μm < TiN size was at least 50% of the
total amount (c) TiN size <0.05 μm was at least 50% of the total amoun
The underline represents the portions outside the range of the present
invention
TABLE 8
__________________________________________________________________________
Processing Condition
Cold Rolling
Hot Rolling Condition
Condition
Thickness Thickness Skin
Slab of Hot
Reduc-
of cold Pass
Sur-
Heating Winding
Rolled
tion
rolled Roll-
face
Temp. Temp.
Sheet Ratio
sheet Annealing Condition
ing
Treat
No.
°C.
°C.
mm % mm System
Cycle % ment
__________________________________________________________________________
18 1250 550 3.0 73 0.8 Box 680° C. × 14
1.2
EG
19 1150 750 3.5 77 0.8 Con.
810° C. × 1
1.0.
EG
20 1250 550 3.0 73 0.8 Box 680° C. × 14
1.2
TC
21 1150 750 3.5 77 0.8 Con.
810° C. × 1
1.0.
TC
22 1250 550 3.0 73 0.8 Box 680° C. × 14
1.2
WU
23 1150 750 3.5 77 0.8 Con.
820° C. × 1
1.0.
WU
__________________________________________________________________________
Properties
This
Yield
Tensile
Elon- invention
strength
strength
gation
r or Comp.
No.
kgf/mm.sup.2
kgf/mm.sup.2
% Value
Example
__________________________________________________________________________
18 17.2 29.7 46 1.82
This
invention
19 18.3 31.2 45 1.73
This
invention
20 18.1 31.1 46 1.79
This
invention
21 18.5 31.8 45 1.75
This
invention
22 17.1 30.1 46 1.76
This
invention
23 17.5 30.6 45 1.73
This
invention
__________________________________________________________________________
Annealing System
Con: Continuous annealing
Box: Box annealing
Surface Treatment
EG: electrogalvanizing
TC: lead plating
WU: electrogalvanizing with organic coating
Steels having the components shown in Table 9 were hot rolled, cold rolled and annealed under the condition tabulated in Table 10, and molten zinc plating was carried out. Properties obtained in these cases were also tabulated in Table 10.
The steel sheets according to the present invention exhibited excellent properties even after the molten zinc plating treatment. By the way, the plating quantity of molten zinc plating was 100 g/m2 per surface.
TABLE 9
__________________________________________________________________________
Si ×
Mn ×
P ×
Al ×
Ti ×
C 10-3
10-3
10-3
S 10-3
N 10-3
B Free N*
TiN**
No.
ppm
% % % ppm
% ppm
% ppm
ppm Form
Remarks
__________________________________________________________________________
24 501
12 222 6 144
60 82
24 -- 12 a Thia invention
25 432
9 237 19 125
35 111
31 17 20 a This invention
__________________________________________________________________________
*Free N: total N Ti/3.42
**TiN form: (a) 0.05 μm ≦ TiN size ≦ 10 μm was at
least 50% of the tatal amount (b) 10 μm < TiN size was at least 50% of
the total amount (c) TiN size < 0.05 μm was at least 50% of the total
amount
The underline represents the portions outside the range of the present
invention
TABLE 10
__________________________________________________________________________
Processing Condition
Cold Rolling
Hot Rolling Condition
Condition
Thickness Thickness Skin
Slab of Hot
Reduc-
of cold Pass
Heating Winding
Rolled
tion
rolled Roll-
Surface
Temp. Temp.
Sheet Ratio
sheet Annealing Condition
ing
Treat-
No.
°C.
°C.
mm % mm System
Cycle % ment
__________________________________________________________________________
24 1150 750 3.5 77 0.8 Con.
810° C. × 1
1.0.
GI
25 1150 550 3.5 77 0.8 Con.
810° C. × 1
1.0.
GI
__________________________________________________________________________
Properties
Yield
Tensile
Elon- This
strength
strength
gation
r invention or
No.
kgf/mm.sup.2
kgf/mm.sup.2
% Value Comp. Example
__________________________________________________________________________
24 24.4 34.1 41 1.69 This
invention
25 25.0 34.7 38 1.66 This
invention
__________________________________________________________________________
Annealing System
Con.: Continuous annealing
Box: Box Annealing
Surface Treatment
GI: molten zinc plating
Steels having the components shown in Table 11 were hot rolled, cold rolled and annealed under the condition tabulated in Table 12, and electrotinning was carried out. Properties obtained in these cases were also tabulated in Table 12.
The steel sheets according to the present invention also exhibited here excellent properties as a steel sheet for a tin plate.
TABLE 11
__________________________________________________________________________
Si ×
Mn ×
P ×
Al ×
Ti ×
C 10-3
10-3
10-3
S 10-3
N 10-3
Free N*
TiN**
No.
ppm
% % % ppm
% ppm
% ppm Form
Remarks
__________________________________________________________________________
26 488
10 258 17 110
52 117
28 35 a This invention
27 488
10 258 17 110
52 117
-- 117 a Comp. Example
28 488
10 258 17 110
52 117
23 50 a This invention
29 488
10 258 17 110
52 117
-- 117 a Comp. Example
__________________________________________________________________________
*Free N: total N Ti/3.42
**TiN form: (a) 0.05 μm ≦ TiN size ≦10 μm was at leas
50% of the tatal amount (b) 10 μm < TiN size was at least 50% of the
total amount (c) TiN size <0.05 μm was at least 50% of the total amoun
The underline represents the portions outside the range of the present
invention
TABLE 12
__________________________________________________________________________
Processing Condition
Cold Rolling
Hot Rolling Condition
Condition
Thicknes Thickness Skin
Slab of Hot
Reduc-
of clod Pass Properties
This
Heating Winding
Rolled
tion
rolled
Annealing roll-
Surface Degree
invention
Temp. Temp.
Sheet ratio
sheet Condition ing
Treat-
Hard-
of or Comp.
No.
°C.
°C.
mm % mm System
Cycle % ment ness
Temper
Example
__________________________________________________________________________
26 1235 550 3.0 90 0.3 Box 650° C. ×
1.3
ET 49 T-1 This
8 H invention
27 1235 550 3.0 90 0.3 Box 650° C. ×
1.3
ET 56 T-1 Comp.
8 H Example
28 1235 550 3.0 90 0.3 Con.
650° C. ×
1.3
ET 61 T-4 This
20 sec. invention
29 1235 550 3.0 90 0.3 Con.
650° C. ×
1.3
ET 68 T-4 Comp.
20 sec. Example
__________________________________________________________________________
*refining rolling: reduction ratio 1.3%
**hardness: rockwell hardness (HR30T)
Steels having the components shown in Table 13 were hot rolled, cold rolled and annealed under the condition tabulated in Table 14. Properties obtained in these cases were also tabulated in Table 14.
Even when those elements which were unavoidably contained in the scrap, such as Sn, Cr, Ni, etc., were contained, the effect of the present invention was not at all deteriorated. In other words, excellent formability could be obtained when the basic components, the quantity of TiN and its form were within the ranges of the present invention.
TABLE 13
__________________________________________________________________________
Si ×
Mn ×
P ×
Al ×
Ti ×
Free
C 10.sup.-3
10.sup.-3
10.sup.-3
S 10.sup.-3
N 10.sup.-3
B N* TiN**
Cu Nl Cr As Sn Mo
NO.
ppm
% % % ppm
% ppm
% ppm
ppm
form
% % % % % % Remarks
__________________________________________________________________________
30 302
9 163 5 118
32 122
29 -- 37 a 0.016
0.026
0.015
-- -- -- This
invention
31 415
8 170 6 135
70 90
0 -- 90 a -- -- -- -- -- -- Comp.
Example
32 432
9 237 19 125
35 111
31 -- 20 a 0.10
0.04
0.08
0.04
0.04
0.05
This
invention
33 302
9 163 5 118
35 122
29 -- 37 a 0.09
0.19
0.19
0.05
0.04
0.06
This
invention
34 401
9 165 6 121
35 118
29 -- 37 b 0.015
0.024
0.024
-- -- -- Comp.
Example
35 415
9 165 6 121
32 118
29 -- 33 c 0.015
0.024
0.024
-- -- -- Comp.
Example
__________________________________________________________________________
*Free N: total N Ti/3.42
**TiN form: (a) 0.05 μm ≦ TiN size ≦10 μm was at leas
50% of the tatal amount (b) 10 μm < TiN size was at least 50% of the
total amount (c) TiN size <0.05 μm was at least 50% of the total amoun
The underline represents the portions outside the range of the present
invention
TABLE 14
__________________________________________________________________________
Processing Condition
Cold Rolling
Hot Rolling Condition
Condition
Thickness Thickness Skin
Slab of Hot
reduc-
of cold Pass
Sur-
Heating Winding
Rolled
tion
rolled Roll-
face
Temp. Temp.
Sheet Ratio
sheet Annealing Condition
ing
Treat
No.
°C.
°C.
mm % mm System
Cycle % ment
__________________________________________________________________________
30 1250 550 3.0 73 0.8 Box 680° C. × 14
1.2
--
31 1250 550 3.0 73 0.8 Box 680° C. × 14
1.2
--
32 1150 750 3.5 77 0.8 Con.
810° C. × 1
1.0.
--
33 1250 550 3.0 73 0.8 Box 680° C. × 14
1.2
--
34 1250 550 3.0 73 0.8 Box 680° C. × 14
1.2
--
35 1250 550 3.0 73 0.8 Box 680° C. × 14
1.2
--
__________________________________________________________________________
Properties
This
Yield
Tensile
Elon- invention
strength
strength
gation
r or Comp.
No.
kgf/mm.sup.2
kgf/mm.sup.2
% value
Example
__________________________________________________________________________
30 17.1 31.0 46 1.81
This
invention
31 19.7 33.4 38 1.52
Comp.
Example
32 18.1 32.8 44 1.68
This
invention
33 17.8 32.4 44 1.70
This
invention
34 17.5 32.8 42 1.66
Comp.
Example
35 25.4 32.4 36 1.39
Comp.
Example
__________________________________________________________________________
Annealing System
Con.: Continuous annealing
Box: Box annealing
The present invention can make N harmless where N unavoidably attains a high level when a scrap is reutilized, and can obtain a cold rolled steel sheet having high formability irrespective of a high N content.
The cold rolled steel sheet according to the present invention can be utilized not only as the cold rolled steel sheet but also as a raw sheet for a surface treated steel sheet such as a molten zinc plated steel sheet, an electrogalvanized steel sheet, an electrotin plated steel sheet, and so forth. Accordingly, the present invention has an extremely great industrial value.
Claims (7)
1. A cold rolled steel sheet having excellent formability and comprising not greater than 0.1 wt % of C, 0.0060 to 0.0150 wt % of N, not greater than 0.4 wt % of Mn (within the range satisfying the relation Mn/S≧7), not greater than 0.030 wt % of S, 0.005 to 0.1% of Al, not greater than 0.08 wt % of Ti (within the range satisfying the relation (N (%)--Ti/3.42 (%)≦0.0070%), and the balance consisting of Fe and unavoidable impurities, wherein TiN having a size of 0.05 to 10 μm is precipitated in a weight of at least 1/2 of the total TiN weight.
2. A cold rolled steel sheet according to claim 1, wherein the Ti content is within the range satisfying the relation N (%)--Ti/3.42 (%)≦0.0040%.
3. A cold rolled steel sheet according to claim 1, wherein the Ti content is within the range satisfying the relation 0.0020%≦N (%)--Ti/3.42 (%)≦0.0070%.
4. A cold rolled steel sheet according to claim 2, which further contains B in an amount satisfying the relation 1.0≦1.3×B (%)/(N (%)--Ti (%)/3.42)≦1.5.
5. A production method of a cold rolled steel sheet having excellent formability by casting a molten steel comprising not greater than 0.1 wt % of C, 0.0060 to 0.0150 wt % of N, not greater than 0.4 wt % of Mn (within the range satisfying the relation Mn/S≧7), not greater than 0.03 wt % of S, 0.005 to 0.1 wt % of Al, not greater than 0.08 wt % of Ti (within the range satisfying the relation (N (%)--Ti/3.42 (%)≦0.0040%), and the balance consisting of Fe and unavoidable impurities, said method comprising:
cooling a resulting slab at a cooling rate of 10° to 50° C./min within the temperature range of a solidifying point to 600° C. so as to precipitate TiN having a size of 0.05 to 10 μm in a weight of at least 1/2 of the total TiN weight in the resulting slab;
heating the slab;
hot rolling the slab;
winding a resulting hot rolled steel strip at a temperature of at least 700° C.;
cold rolling the hot rolled steel strip;
and
effecting then continuous annealing.
6. A production method of a cold rolled steel sheet having excellent formability, by casting a molten steel comprising not greater than 0.1 wt % of C, 0.0060 to 0.0150 wt % of N, not greater than 0.4 wt % of Mn (within the range satisfying the relation Mn/S≧7), not greater than 0.03 wt % of S, 0.005 to 0.1 wt % of Al, not greater than 0.08 wt % of Ti (within the range satisfying the relation (N (%)--Ti/3.42 (%)≦0.0040%), B in an amount satisfying the relation 1.0≦1.3×B (%)/(N (%)--Ti (%)/3.42)≦1.5 and the balance consisting of Fe and unavoidable impurities, said method comprising:
cooling a resulting slab at a cooling rate of 10° to 50° C./min within the temperature range of a solidifying point to 600° C. so as to precipitate TiN having a size of 0.05 to 10 μm in a weight of at least 1/2 of the total TiN weight in the resulting slab;
heating the slab;
hot rolling the slab;
winding a resulting hot rolled steel strip;
cold rolling the hot rolled steel strip;
and
effecting then continuous annealing.
7. A production method of a cold rolled steel sheet having excellent formability, by casting a molten steel comprising not greater than 0.1 wt % of C, 0.0060 to 0.0150 wt % of N, not greater than 0.4 wt % of Mn (within the range satisfying the relation Mn/S≧7), not greater than 0.030 wt % of S, 0.005 to 0.1 wt % of Al, not greater than 0.08 wt % of Ti (within the range satisfying the relation 0.0020 wt %≦N (%)--Ti/3.42 (%)≦0.0070%), and the balance consisting of Fe and unavoidable impurities, said method comprising:
cooling a resulting slab at a cooling rate of 10° to 50° C./min within a temperature range of a solidifying point to 600° C. so as to precipitate TiN having a size of 0.05 to 10 μm in a weight of at least 1/2 of the TiN total weight inside the resulting slab;
heating the slab to a temperature of not lower than 1,130° C.;
hot rolling the slab;
winding a resulting hot rolled steel strip within a temperature range of not higher than 650° C.;
cold rolling the hot rolled steel strip;
and
effecting then box annealing.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP26024793A JP3314833B2 (en) | 1993-10-18 | 1993-10-18 | Cold rolled steel sheet excellent in workability and method for producing the same |
| JP5-260247 | 1993-10-18 | ||
| PCT/JP1994/001752 WO1995011320A1 (en) | 1993-10-18 | 1994-10-18 | Cold-rolled steel sheet having excellent workability and process for producing the same |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US5558726A true US5558726A (en) | 1996-09-24 |
Family
ID=17345402
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US08/481,426 Expired - Lifetime US5558726A (en) | 1993-10-18 | 1994-10-18 | Cold rolled steel having excellent machinability and production thereof |
Country Status (10)
| Country | Link |
|---|---|
| US (1) | US5558726A (en) |
| JP (1) | JP3314833B2 (en) |
| KR (1) | KR0173499B1 (en) |
| CN (1) | CN1040776C (en) |
| CA (1) | CA2151951C (en) |
| DE (2) | DE4497994C2 (en) |
| GB (1) | GB2289057B (en) |
| MY (1) | MY112255A (en) |
| TW (1) | TW310345B (en) |
| WO (1) | WO1995011320A1 (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5928442A (en) * | 1997-08-22 | 1999-07-27 | Snap-On Technologies, Inc. | Medium/high carbon low alloy steel for warm/cold forming |
| US5961747A (en) * | 1997-11-17 | 1999-10-05 | University Of Pittsburgh | Tin-bearing free-machining steel |
| US6200395B1 (en) | 1997-11-17 | 2001-03-13 | University Of Pittsburgh - Of The Commonwealth System Of Higher Education | Free-machining steels containing tin antimony and/or arsenic |
| US6206983B1 (en) | 1999-05-26 | 2001-03-27 | University Of Pittsburgh - Of The Commonwealth System Of Higher Education | Medium carbon steels and low alloy steels with enhanced machinability |
| US6217675B1 (en) * | 1998-06-30 | 2001-04-17 | Nippon Steel Corporation | Cold rolled steel sheet having improved bake hardenability |
| US20030121576A1 (en) * | 2001-02-07 | 2003-07-03 | Nkk Corporation | Steel sheet and method for manufacturing the same |
Families Citing this family (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0709480B1 (en) * | 1994-03-29 | 2001-06-13 | Nippon Steel Corporation | Steel plate excellent in prevention of brittle crack propagation and low-temperature toughness and process for producing the plate |
| DE19834361A1 (en) * | 1998-07-30 | 2000-02-03 | Schaeffler Waelzlager Ohg | Precision deep-drawn case-hardened component, especially a roller bearing and motor component e.g. a needle bearing, sleeve or bush, is made from a cold rolled strip of steel with specified titanium, nitrogen and low aluminum contents |
| AUPP811399A0 (en) * | 1999-01-12 | 1999-02-04 | Bhp Steel (Jla) Pty Limited | Cold rolled steel |
| US6840434B2 (en) | 2002-04-09 | 2005-01-11 | Ford Motor Company | Tin-and zinc-based solder fillers for aluminum body parts and methods of applying the same |
| WO2017010064A1 (en) * | 2015-07-10 | 2017-01-19 | Ｊｆｅスチール株式会社 | Cold rolled steel sheet and method for producing same |
| CN111118387B (en) * | 2019-12-13 | 2021-07-23 | 河钢乐亭钢铁有限公司 | Method for improving surface quality of boron-containing steel continuous casting slab |
| CN111647821B (en) * | 2020-07-08 | 2021-10-29 | 马鞍山钢铁股份有限公司 | A kind of yield strength 550MPa grade hot-dip galvanized steel sheet and production method thereof |
| KR20250024732A (en) | 2023-08-09 | 2025-02-19 | 주식회사 포스코 | Steel sheet and method for manufacturing thereof |
| KR20250094526A (en) | 2023-12-15 | 2025-06-25 | 주식회사 포스코 | Steel sheet and method for manufacturing thereof |
| KR20250093739A (en) | 2023-12-15 | 2025-06-25 | 주식회사 포스코 | Cold rolled steel sheet and manufacturing method thereof |
| KR20250094525A (en) | 2023-12-15 | 2025-06-25 | 주식회사 포스코 | Steel sheet and method for manufacturing thereof |
| KR20250094524A (en) | 2023-12-15 | 2025-06-25 | 주식회사 포스코 | Steel sheet and method for manufacturing thereof |
| KR20250093063A (en) | 2023-12-15 | 2025-06-24 | 주식회사 포스코 | Cold-rolled steel sheet and method for manufacturing thereof |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5312899B2 (en) * | 1971-10-26 | 1978-05-06 | ||
| JPS5726124A (en) * | 1980-07-19 | 1982-02-12 | Nippon Steel Corp | Production of cold rolled steel plate of excellent sand burning hardenability |
| JPS6345322A (en) * | 1986-08-09 | 1988-02-26 | Sumitomo Metal Ind Ltd | Production of steel sheet for enamel |
| JPH03267321A (en) * | 1990-03-16 | 1991-11-28 | Nippon Steel Corp | Manufacturing method of cold rolled steel sheet for deep drawing |
| US5123969A (en) * | 1991-02-01 | 1992-06-23 | China Steel Corp. Ltd. | Bake-hardening cold-rolled steel sheet having dual-phase structure and process for manufacturing it |
| JPH04292352A (en) * | 1991-03-18 | 1992-10-16 | Olympus Optical Co Ltd | Card conveying device |
| JPH06136482A (en) * | 1992-09-14 | 1994-05-17 | Japan Casting & Forging Corp | Hot rolled steel sheet having >=34kgf/mm2 tensile strength and excellent in uniform elongation after cold working and its production |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3625780A (en) * | 1968-04-29 | 1971-12-07 | Youngstown Sheet And Tube Co | Process for preparation of high-strength alloy of titanium and ferritic structure |
| JPS5967322A (en) * | 1982-10-08 | 1984-04-17 | Kawasaki Steel Corp | Manufacture of cold rolled steel plate for deep drawing |
-
1993
- 1993-10-18 JP JP26024793A patent/JP3314833B2/en not_active Expired - Lifetime
-
1994
- 1994-10-17 MY MYPI94002768A patent/MY112255A/en unknown
- 1994-10-18 KR KR1019950702441A patent/KR0173499B1/en not_active Expired - Lifetime
- 1994-10-18 DE DE19944497994 patent/DE4497994C2/en not_active Expired - Lifetime
- 1994-10-18 WO PCT/JP1994/001752 patent/WO1995011320A1/en not_active Ceased
- 1994-10-18 US US08/481,426 patent/US5558726A/en not_active Expired - Lifetime
- 1994-10-18 CA CA 2151951 patent/CA2151951C/en not_active Expired - Lifetime
- 1994-10-18 DE DE19944497994 patent/DE4497994T1/en active Pending
- 1994-10-18 CN CN94190795A patent/CN1040776C/en not_active Expired - Lifetime
- 1994-10-18 TW TW83109664A patent/TW310345B/zh not_active IP Right Cessation
- 1994-10-18 GB GB9512305A patent/GB2289057B/en not_active Expired - Lifetime
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5312899B2 (en) * | 1971-10-26 | 1978-05-06 | ||
| JPS5726124A (en) * | 1980-07-19 | 1982-02-12 | Nippon Steel Corp | Production of cold rolled steel plate of excellent sand burning hardenability |
| JPS6345322A (en) * | 1986-08-09 | 1988-02-26 | Sumitomo Metal Ind Ltd | Production of steel sheet for enamel |
| JPH03267321A (en) * | 1990-03-16 | 1991-11-28 | Nippon Steel Corp | Manufacturing method of cold rolled steel sheet for deep drawing |
| US5123969A (en) * | 1991-02-01 | 1992-06-23 | China Steel Corp. Ltd. | Bake-hardening cold-rolled steel sheet having dual-phase structure and process for manufacturing it |
| JPH04292352A (en) * | 1991-03-18 | 1992-10-16 | Olympus Optical Co Ltd | Card conveying device |
| JPH06136482A (en) * | 1992-09-14 | 1994-05-17 | Japan Casting & Forging Corp | Hot rolled steel sheet having >=34kgf/mm2 tensile strength and excellent in uniform elongation after cold working and its production |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5928442A (en) * | 1997-08-22 | 1999-07-27 | Snap-On Technologies, Inc. | Medium/high carbon low alloy steel for warm/cold forming |
| US5961747A (en) * | 1997-11-17 | 1999-10-05 | University Of Pittsburgh | Tin-bearing free-machining steel |
| US6200395B1 (en) | 1997-11-17 | 2001-03-13 | University Of Pittsburgh - Of The Commonwealth System Of Higher Education | Free-machining steels containing tin antimony and/or arsenic |
| US6217675B1 (en) * | 1998-06-30 | 2001-04-17 | Nippon Steel Corporation | Cold rolled steel sheet having improved bake hardenability |
| AU749441B2 (en) * | 1998-06-30 | 2002-06-27 | Nippon Steel Corporation | Cold rolled steel sheet excellent in baking hardenability |
| US6206983B1 (en) | 1999-05-26 | 2001-03-27 | University Of Pittsburgh - Of The Commonwealth System Of Higher Education | Medium carbon steels and low alloy steels with enhanced machinability |
| US20030121576A1 (en) * | 2001-02-07 | 2003-07-03 | Nkk Corporation | Steel sheet and method for manufacturing the same |
| US6767417B2 (en) * | 2001-02-07 | 2004-07-27 | Nkk Corporation | Steel sheet and method for manufacturing the same |
| EP1359235A4 (en) * | 2001-02-07 | 2005-01-12 | Jfe Steel Corp | Thin steel sheet and method for production thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH07118795A (en) | 1995-05-09 |
| CA2151951C (en) | 1999-09-07 |
| KR950704531A (en) | 1995-11-20 |
| CA2151951A1 (en) | 1995-04-27 |
| KR0173499B1 (en) | 1999-02-18 |
| GB9512305D0 (en) | 1995-09-06 |
| WO1995011320A1 (en) | 1995-04-27 |
| TW310345B (en) | 1997-07-11 |
| DE4497994T1 (en) | 1995-12-21 |
| MY112255A (en) | 2001-05-31 |
| CN1040776C (en) | 1998-11-18 |
| DE4497994C2 (en) | 2001-03-01 |
| JP3314833B2 (en) | 2002-08-19 |
| CN1115991A (en) | 1996-01-31 |
| GB2289057A (en) | 1995-11-08 |
| GB2289057B (en) | 1997-04-09 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US5558726A (en) | Cold rolled steel having excellent machinability and production thereof | |
| US5624504A (en) | Duplex structure stainless steel having high strength and elongation and a process for producing the steel | |
| JP4811528B2 (en) | High-strength cold-rolled steel sheet and manufacturing method thereof | |
| KR20100070375A (en) | High-strength cold-rolled steel sheet | |
| US20090071574A1 (en) | Cold rolled dual phase steel sheet having high formability and method of making the same | |
| KR20020037339A (en) | High resistance steel band or sheet and method for the production thereof | |
| US5415711A (en) | High-strength spring steels and method of producing the same | |
| CN107557671B (en) | Microalloyed spring steel and preparation method thereof | |
| WO2022063244A1 (en) | 700 mpa grade hot-formed axle housing steel and preparation method therefor | |
| GB2133805A (en) | Ferrite-bainite cast iron with nodular graphite | |
| US3925111A (en) | High tensile strength and steel and method for manufacturing same | |
| JP3350285B2 (en) | Manufacturing method of non-oriented electrical steel sheet with excellent surface properties and magnetic properties | |
| KR100742939B1 (en) | Non-aging cold rolled steel sheet with high yield ratio and its manufacturing method | |
| CN1050903A (en) | Improve the method for the cold formability of heat-treated steel | |
| JP5189959B2 (en) | High strength cold-rolled steel sheet with excellent elongation and stretch flangeability | |
| EP4261313A1 (en) | High-strength wire rod for cold heading, having excellent heat treatment characteristics and hydrogen delayed fracture characteristics, heat treatment component, and manufacturing methods therefor | |
| EP3831978A1 (en) | Ti- and nb-added ferritic stainless steel excellent in low-temperature toughness of welds | |
| CN114000053A (en) | Hot-rolled steel sheet and method for producing same | |
| JP5717631B2 (en) | Cold-rolled steel sheet manufacturing method and cold-rolled steel sheet excellent in press formability | |
| CN113957358A (en) | High-strength thermoforming steel substrate with tensile strength greater than 2200 MPa and preparation method thereof | |
| JP3918589B2 (en) | Steel plate for heat treatment and manufacturing method thereof | |
| CN115584428B (en) | A kind of short-process low-cost cold-rolled DH590 steel and its production method | |
| CN110066966A (en) | A kind of low internal stress titaniferous high-strength steel and production method | |
| JPH06235047A (en) | High strength cold rolled steel sheet excellent in cold workability and its production | |
| CN115679207B (en) | Steel plate for automobiles and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| AS | Assignment |
Owner name: JAPAN CASTING & FORGING CORPORATION, JAPAN Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:YATOH, HISAYOSHI;YAMASHITA, YASUHIKO;HARABUCHI, TAKASHI;AND OTHERS;REEL/FRAME:007620/0841 Effective date: 19950526 Owner name: NIPPON STEEL CORPORATION, JAPAN Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:YATOH, HISAYOSHI;YAMASHITA, YASUHIKO;HARABUCHI, TAKASHI;AND OTHERS;REEL/FRAME:007620/0841 Effective date: 19950526 |
|
| STCF | Information on status: patent grant |
Free format text: PATENTED CASE |
|
| CC | Certificate of correction | ||
| FEPP | Fee payment procedure |
Free format text: PAYOR NUMBER ASSIGNED (ORIGINAL EVENT CODE: ASPN); ENTITY STATUS OF PATENT OWNER: LARGE ENTITY |
|
| FPAY | Fee payment |
Year of fee payment: 4 |
|
| AS | Assignment |
Owner name: NIPPON STEEL CORPORATION, JAPAN Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNOR:JAPAN CASTING & FORGING CORPORATION;REEL/FRAME:012343/0713 Effective date: 20010907 |
|
| FPAY | Fee payment |
Year of fee payment: 8 |
|
| FPAY | Fee payment |
Year of fee payment: 12 |